N-Haloacetylphenylamino carbonyl cyclic intermediates

ABSTRACT

Novel N-haloacetylphenylamino carbonyl oximes represented by the formula ##STR1## wherein Ar is phenyl or substituted phenyl; R 1  is halomethyl; R 2  and R 3  are each independently hydrogen, alkyl, phenyl, benzyl, substituted phenyl or benzyl, haloalkyl, cyanoalkyl, alkoxyalkyl, alkylthioalkyl or thiocyanoalkyl; R 4  is hydrogen or alkyl; n is 0 or 1; m is 0 or 1; R is hydrogen, alkyl, alkenyl, alkynyl, alkylthioalkyl, haloalkyl, alkoxyalkyl, cyanoalkyl, phenyl, benzyl, substituted phenyl or benzyl, or R is acyl of the formula ##STR2## wherein R 5  is hydrogen, alkyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, alkoxy, alkylthio, acetonyl, or the group --NR&#39;R&#34; wherein R&#39; and R&#34; are independently hydrogen, alkyl or phenyl; with the proviso that R 2  and R 3  may be joined together to form a carbocyclic ring or a heterocyclic ring; or R and R 2  may be joined together to form a heterocyclic ring; or R and R 3  may be joined together to form a heterocyclic ring.

RELATED APPLICATION

This application is a division of Ser. No. 14,410, filed Feb. 23, 1979,now U.S. Pat. No. 4,260,410, which in turn is a continuation-in-part ofapplication Ser. No. 892,365, filed Mar. 31, 1978, now U.S. Pat. No.4,174,210.

DESCRIPTION OF THE PRIOR ART

U.S. Pat. No. 3,976,471, issued on Aug. 24, 1976, to S. B. Richterdiscloses herbicidalN-(alkylideneaminooxymethyl)-alpha-haloacetanilides.

U.S. Pat. No. 3,966,811, issued on June 29, 1976, to J. Krenzer,discloses herbicidal dialkylacetals of anilinoacetaldehydes.

DESCRIPTION OF THE INVENTION

The compounds of the invention are represented by the formula ##STR3##wherein Ar is phenyl or phenyl substituted with 1 to 4 of the same ordifferent substituents selected from fluoro, chloro, bromo, iodo, oralkyl of 1 to 4 carbon atoms, or substituted with 1 to 2 of the same ordifferent substituents selected from alkoxy of 1 to 4 carbon atoms,nitro or haloalkyl of 1 to 2 carbon atoms and 1 to 3 of the same ordifferent halogens selected from fluoro, chloro, bromo or iodo;

R¹ is halomethyl of 1 to 3 of the same or different halogens selectedfrom fluoro, chloro, bromo or iodo;

R² and R³ are each independently hydrogen, alkyl of 1 to 6 carbon atoms,phenyl, benzyl, phenyl or benzyl substituted with 1 to 2 of the same ordifferent substituents selected from fluoro, chloro, bromo, iodo, alkylof 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or nitro;haloalkyl of 1 to 4 carbon atoms and 1 to 10 of the same or differenthalogens selected from fluoro, chloro, bromo or iodo, cyanoalkyl of 2 to6 carbon atoms, alkoxyalkyl of 2 to 6 carbon atoms, alkylthioalkyl of 2to 6 carbon atoms, or thiocyanoalkyl of 2 to 6 carbon atoms;

R⁴ is hydrogen or alkyl of 1 to 6 carbon atoms;

n is 0 or 1;

m is 0 or 1;

R is hydrogen, alkyl of 1 to 6 carbon atoms, alkenyl of 3 to 6 carbonatoms, alkynyl of 3 to 6 carbon atoms, alkylthio of 2 to 6 carbon atoms,haloalkyl of 1 to 4 carbon atoms and 1 to 10 of the same or differenthalogens selected from fluoro, chloro, bromo or iodo, alkoxyalkyl of 2to 6 carbon atoms, cyanoalkyl of 2 to 6 carbon atoms, phenyl, benzyl,phenyl or benzyl substituted with 1 to 2 of the same or differentsubstituents selected from fluoro, chloro, bromo, iodo, alkyl of 1 to 4carbon atoms, alkoxy of 1 to 4 carbon atoms or nitro, or R is acyl ofthe formula ##STR4## wherein R⁵ is hydrogen, alkyl of 1 to 4 carbonatoms, haloalkyl of 1 to 4 carbon atoms and 1 to 10 of the same ordifferent halogens selected from fluoro, bromo, chloro or iodo,alkoxyalkyl of 2 to 6 carbon atoms, alkylthioalkyl of 2 to 6 carbonatoms, alkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms,acetonyl, or the group --NR'R" wherein R' and R" are independentlyhydrogen, alkyl of 1 to 6 carbon atoms or phenyl;

with the proviso that R² and R³ may be joined together to form acarbocyclic ring of 5 to 6 carbon atoms or a heterocyclic ringcontaining one O, N or S hetero atom and 4 to 5 carbon atoms; or R andR² may be joined together to form a heterocyclic ring containing 3 or 4carbon atoms; or R and R³ may be joined together to form a heterocyclicring containing 3 or 4 carbon atoms.

Representative Ar groups include 2-fluorophenyl, 2-chlorophenyl,2,3-dichlorophenyl, 2-trifluoromethylphenyl, 3-bromophenyl,3,5-diiodophenyl, 2-methylphenyl, 2-methyl-3-chlorophenyl,2,3-dimethylphenyl, 2,3,5,6-tetramethylphenyl, 2,6-diethylphenyl,2-methyl-6-ethylphenyl, 2,3,6-trimethylphenyl, 3,5-dimethylphenyl,2-nitrophenyl and 2-ethoxyphenyl. The substituents on the phenyl ringare preferably in the 2-, 3-, 5- and 6-positions, and most preferablyare in the 2- and 6-positions.

Representative R¹ groups include fluoromethyl, chloromethyl,bromomethyl, iodomethyl, dichloromethyl, tribromomethyl andfluorodichloromethyl.

Representative alkyl R, R² and R³ are methyl, ethyl, isopropyl andn-hexyl.

Representative alkenyl R groups are allyl, 2-butenyl and 3-hexenyl.Representative alkynyl R groups are propargyl, 3-butynyl and 2-pentynyl.Representative substituted-phenyl R, R² and R³ groups include3-fluorophenyl, 2-chlorophenyl, 4-bromophenyl, 2-iodophenyl,3-methylphenyl, 2,4-diethylphenyl, 3-methoxyphenyl and 2-nitrophenyl.Representative substituted-benzyl R, R² and R³ groups include4-chlorobenzyl, 2-methoxybenzyl, 2,4-dimethylbenzyl, 3-nitrobenzyl, etc.

Representative R, R², R³ and R⁵ haloalkyl groups includetrichloromethyl, 1,1,2,2-tetrachloroethyl and fluoromethyl.Representative R, R² and R³ cyanoalkyl groups include cyanomethyl andcyanoethyl. Representative R, R², R³ and R⁵ alkoxyalkyl groups includemethoxymethyl, ethoxymethyl and methoxyethyl. Representative R, R², R³and R⁵ alkylthioalkyl groups include methylthiomethyl, ethylthiomethyland methylthioethyl. Representative R² and R³ thiocyanoalkyl groupsinclude thiocyanomethyl and thiocyanoethyl.

Preferred substituted phenyl R, R² and R³ groups are phenyl substitutedwith 1to 2 fluoro, chloro, bromo or alkyl of 1 to 4 carbon atoms.

Representative groups in which R² and R³ are joined together to formpart of a ring include dimethylene, trimethylene, tetramethylene, --CH₂OCH₂ --, --CH₂ ═N--CH₂ --, --CH₂ SCH₂ --, --CH₂ CH₂ OCH₂ --, --CH₂ NHCH₂--, etc.

Representative R⁵ groups include hydrogen, methyl, ethyl, isopropyl,trichloromethyl, fluoromethyl, methoxymethyl, methylthiomethyl, methoxy,ethoxy, methylthio, ethylthio, amino, methylamino, dimethylamino andanilino.

Representative R⁴ groups include hydrogen, methyl and ethyl. PreferablyR⁴ is hydrogen.

Representative groups in which R and R² are joined include --CH₂ -- and--CH₂ CH₂ --.

Representative groups in which R and R³ are joined include --CH₂ CH₂ --and --CH₂ CH₂ CH₂ --.

Preferably m=1 when n=0 and m=0 when n=1.

Preferably Ar is phenyl substituted with 2 to 3 alkyl of 1 to 4 carbonatoms. Most preferably Ar is 2,6-dialkylphenyl, especially2,6-dimethylphenyl and 2,6-diethylphenyl.

Preferably R¹ is monohalomethyl, especially chloromethyl or bromomethyl.

Preferably R² and R³ individually are hydrogen or alkyl of 1 to 3 carbonatoms or are joined together to form part of a 5- or 6-memberedcarbocyclic ring, that is, R² and R³ are dimethylene, trimethylene ortetramethylene.

Preferably R is hydrogen or alkyl of 1 to 6 carbon atoms. Mostpreferably R is alkyl of 1 to 3 carbon atoms.

When m=0 and n=1, R and R³ are both preferably alkyl of 1 to 3 carbonatoms, most preferably methyl.

The oxime compounds of the invention are prepared by reaction of thecarbonyl compound (II) and an alkoxyamino compound (III) by conventionalprocedures, as depicted in reaction (1): ##STR5## wherein R, R¹, R², R³,R⁴, n and m have the same meaning as previously defined.

Reaction (1) is generally conducted by reacting substantially equimolaramounts of the carbonyl compound (II) and the alkoxyamino compound (III)in the liquid phase in an inert diluent at a temperature of 0° to 100°C. Generally, the alkoxyamino compound is generated in situ from thecorresponding alkoxyamino hydrochloride salt, e.g., hydroxylaminehydrochloride or methoxyamine hydrochloride, and a base, e.g., aninorganic alkali metal carbonate such as potassium carbonate or atrialkyl amine such as triethylamine.

The N-haloacetylanilino-substituted carbonyl compound (II) is generallyprepared by acylating the anilino-substituted carbonyl compound with ahaloacetyl halide as depicted in reaction (2): ##STR6## wherein R¹, R²,R³, R⁴, n and m have the same meaning as previously defined, and X ischloro or bromo.

The acylation reaction (2) is conducted by conventional procedures. Thereactants (IV) and (V) are generally contacted in substantiallyequimolar amounts in an inert organic solvent at a temperature of 0° to100° C. Suitable inert organic solvents include ethyl acetate,dichloromethane, dimethoxymethane, benzene, etc. If desired, a base suchas a trialkylamine or a pyridine compound may be employed to scavengethe hydrogen halide by-product. The product (II) is isolated andpurified by conventional procedures such as extraction, distillation,chromatography, crystallization, etc.

The carbonyl compound (II) is prepared by a variety of methods. Onemethod for preparing compounds of formula (II) is depicted in thefollowing reaction (3): ##STR7## wherein Ar, R², R³, R⁴, X, m and n havethe same meaning as previously defined.

Reaction (3) is the alkylation of an aniline compound (VI) with analpha-halo or beta-halo carbonyl compound (VII). The alkylation reactionis conducted by more-or-less conventional procedures. For example, thereaction is generally conducted by contacting substantially equimolaramounts of the aniline compound (VI) and the alpha-halo or beta-halocarbonyl compound (VII) in the liquid phase in an inert organic diluentat a temperature of 25° C. to 150° C. Reaction (3) is preferablyconducted with an alpha-bromo carbonyl compound.

A method of preparing anilino-carbonyl compounds of formula (II) whereinn is zero comprises the reaction of an aniline compound (VI) with analpha-hydroxy carbonyl compound to give the carbonyl compound (IX), asdepicted in the following reaction (4): ##STR8## wherein Ar, R² and R³have the same meaning as previously defined.

Reaction (4) is conducted by reacting substantially equimolar amounts ofthe aniline compound (VI) and alpha-hydroxy carbonyl compound (VIII) inthe liquid phase in an inert diluent at a temperature of 25° to 150° C.Water is a by-product of the reaction, and the reaction is generallydriven to completion by removing the water as it is formed in thereaction, for example as an azeotropic distillation with benzene.Reaction (4) is preferably conducted with alpha-hydroxy ketones, e.g.,compounds of formula (VIII) wherein R² is alkyl or aryl. Mostpreferably, the reaction is conducted with compounds of formula (VIII)wherein both R² and R³ are alkyl.

Another method of preparing compounds of formula (II) wherein n is zerois depicted by the following reaction sequence (5): ##STR9## wherein Ar,R¹, R², R³ and X have the same meaning as previously defined.

Reaction (5a) comprises the reaction of the aniline compound (VI) withan epoxide (X) to give the anilino-alcohol (XI). The reaction of theaniline compound (VI) and the epoxide (X) is conducted by contactingsubstantially equimolar amounts of the reactants in the liquid phase,generally in an inert diluent, at a temperature of 0° C. to 100° C.until the reaction is complete. Reaction 5(b) comprises thebis-acylation of the anilino-alcohol to give the acetanilide-ester (XII)by conventional procedures. Reaction (5c) comprises the cleavage of theester group of the acetonilide ester (XII) to give the hydroxyacetanilide compound (XIII). Reaction (5d) comprises the oxidation ofthe hydroxy acetanilide compound (XIII) to the carbonyl compound (XIV)with conventional oxidizing agents, e.g., potassium permanganate,chromium trioxide in pyridine, etc.

An alternate method of making compounds of the invention, particularlywherein R is other than hydrogen or alkyl, is to make the oxime (XV) oracylated oxime (XVI) as shown below under the general conditionsdescribed above for reaction (1): ##STR10##

By conventional procedures, the acylated oxime (XVI) can be reacted withreagents such as phenylisocyanate, methylisocyanate, benzyl bromide,allyl bromide, etc., to directly yield compounds of the inventionwherein R is ##STR11## respectively. Alternatively, these reagents canbe reacted with the oxime (XV), followed by acylation according to thegeneral conditions described above for reaction (2).

The preferred procedure for making compounds of the invention wherein R³is methyl, m=0 and n=1 is as follows: ##STR12##

Reaction (8) is a conventional acylation and can be carried out underconditions described for reaction (2) described above. Reaction (9) canbe carried out by reacting substantially equimolar amounts of the amide(XVII) with propargyl bromide (XVIII) in aqueous solution in thepresence of a base scavenger and a phase-transfer catalyst, such astetrabutyl ammonium bromide, at ambient temperature. The hydrationreaction (10) can be carried out in an aqueous acidic organic solvent,such as aqueous formic acid, in the presence of a catalyst, such asmercuric oxide. Reaction (11) is a conventional oxime formation and canbe conducted under conditions described above for reaction (1).

EXAMPLES Example 1--Preparation of2-(2,6-dimethylphenylamino)cyclopentanol

A solution of 8.4 g (0.1 mol) cyclopentane-1,2-oxide and 12.1 g (0.1mol) 2,6-dimethylaniline in 100 ml toluene was mixed with 6 drops ofboron trifluoride etherate. The solution was heated under reflux for 2hours and then evaporated under reduced pressure to give an oil residue.The residue was chromatographed on 120 g of silica gel usingsuccessively as eluant 1 liter dichloromethane, 1 liter 5% acetone indichloromethane and 1 liter 10% acetone in dichloromethane.2-(2,6-dimethylphenylamino)cyclopentanol (11 g) was the second materialeluted. Elemental analysis of this product (a pale yellow oil) for C₁₃H₁₉ NO showed:

    ______________________________________                                                     Calc.                                                                              Found                                                       ______________________________________                                        % C            76.1   76.5                                                    % H            9.3    9.9                                                     % N            6.8    6.4                                                     ______________________________________                                    

Example 2--Preparation of2-(N-chloroacetyl-2,6-dimethylphenylamino)cyclopentanone

A solution of 7.1 g (0.035 mol) 2-(2,6-dimethylphenylamino)cyclopentanoland 9.4 g (0.083 mol) chloroacetyl chloride in about 200 ml toluene wasstirred at about 25° C. for 20 hours and then heated under reflux for1.5 hours. The reaction mixture was cooled and evaporated under reducedpressure to give an amber oil. The oil was chromatographed on 60 gsilica gel using ethyl ether. The eluted oil product (7.4 g)crystallized on standing. Recrystallization from ethyl ether/hexane gave1-chloroacetoxy-2-(N-chloroacetyl-2,6-dimethylphenylamino)cyclopentane,as a white solid, m.p. 96°-98° C. Elemental analysis for C₁₇ H₂₁ Cl₂ NO₃showed: %Cl, calc. 19.8, found 19.7.

A slurry of 5 g of1-chloroacetoxy-2-(N-chloroacetyl-2,6-dimethylphenylamino)cyclopentaneand 1 g of potassium carbonate in 100 ml ethanol was stirred at 0°-10°C. (ice bath) for 2 hours. The reaction mixture was then filtered andevaporated under reduced pressure to give an oily residue. The residuewas taken up in ethyl ether, washed with water, dried over magnesiumsulfate and evaporated under reduced pressure to give 4 g of2-(N-chloroacetyl-2,6-dimethylphenylamino)cyclopentanol, as a pale amberoil. Elemental analysis for C₁₅ H₂₀ ClNO₂ showed: %Cl, calc. 12.6, found12.9.

A 4.5-ml (0.004-mol) sample of Jones Reagent (26.72 g chromium trioxidein 23 ml of concentrated sulfuric acid diluted with H₂ O to 100 ml) wasadded dropwise to a vigorously stirred solution of 4.4 g (0.016 mol)2-(N-chloroacetyl-2,6-dimethylphenylamino)cyclopentanol in 100 mlacetone. The acetone solution was decanted from the solids, dried overmagnesium sulfate, treated with silica and evaporated under reducedpressure to give 3.7 g of pale yellow oil. The oil was chromatographedon silica gel using mixtures of ethyl ether/hexane as eluant.2-(N-chloroacetyl-2,6-dimethylphenylamino)cyclopentanone was eluted with25% ethyl ether/hexane, as a white solid. This product melted at 79°-82°C. after recrystallization from hexane. This product is tabulated inTable I, as Compound No. 1-A.

Example 3--Preparation of2-(N-chloroacetyl-2,6-dimethylphenylamino)cyclopentanone O-methyloxime

A solution of 3 g (0.01 mol)2-(N-chloroacetyl-2,6-dimethylphenylamino)cyclopentanone, 1.5 g (0.015mol) triethylamine and 1.25 g (0.015 mol) methoxyamine hydrochloride in75 ml ethanol was treated under reflux for 16 hours. After standing atroom temperature for 4 days, the reaction mixture evaporated underreduced pressure to give a solid residue. The solid was partitionedbetween dichloromethane and water. The water layer was extracted withdichloromethane and the combined dichloromethane solutions were driedover magnesium sulfate and evaporated under reduced pressure to give abrown oil. The oil was crystallized from ethyl ether/hexane to give 0.57g of 2,6-dimethyl-alpha-chloroacetanilide as a by-product. The motherliquor was concentrated and chromatographed on silica gel usingdichloromethane as an eluant. The eluted material (1.7 g) crystallizedon standing to give the desired O-methyloxime product as a white solid,m.p. 57°-59° C. This product is tabulated in Table I as Compound No.1-B.

Example 4--Preparation of 3-(N-chloroacetyl2,6-dimethylphenylamino)-2-butanone

A mixture of 121 g (1 mol) dimethylaniline, 149 g (1 mol)3-bromo-2-butanone and 126 g (1.5 mol) sodium bicarbonate in 500 mlethanol was stirred at 60°-70° C. for about 18 hours. The reactionmixture was filtered and the filtrate evaporated under reduced pressureto give an oil. The oil was taken up in dichloromethane, dried overmagnesium sulfate, treated with silica, filtered and evaporated underreduced pressure to give 174.8 g 3-(2,6-dimethylphenylamino)-2-butanoneas a light amber oil. The infrared spectrum of the product showed strongcarbonyl absorption at 5.8 microns.

A 152.6-g (1.36-mol) sample of chloroacetyl chloride was added over 0.25hour in small portions to a stirred solution of 170.8 g (0.89 mol)3-(2,6-dimethylphenylamino)-2-butanone in 500 ml toluene. The reactionmixture was heated under reflux for 3 hours, cooled and filtered. Thefiltrate was concentrated and chromatographed on silica gel usingdichloromethane eluant. The eluted material was recrystallized severaltimes from ethyl ether/hexane to give the3-(N-chloroacetyl-2,6-dimethylphenylamino)-2-butanone product, as abrown solid, m.p. 78°-82° C. The infrared spectrum of the product showedstrong carbonyl absorption at 5.8 and 6.1 microns. This product istabulated in Table I as Compound No. 5-A.

Example 5--Preparation of3-(N-chloroacetyl-2,6-dimethylphenylamino)-2-butanone O-methyloxime

To 10 g (0.037 mol)3-(N-chloroacetyl-2,6-dimethylphenylamino)-2-butanone in 75 ml ethanolwere added 6.2 g methoxyamine hydrochloride, 10.2 g potassium carbonateand 20 cc 4-Angstrom molecular sieves. The resulting mixture was allowedto stir at 25° C. for about 18 hours. The mixture was filtered andevaporated under reduced pressure to give 7.5 g of an oil. The oil wastaken up in ethyl ether and cooled to crystallize out 1.8 g of3-(N-chloroacetyl-2,6-dimethylphenylamino)-2-butanone. Hexane was addedto the mother liquor and cooling crystallized out an additional 1.5 g of3-(N-chloroacetyl-2,6-dimethylphenylamino)-2-butanone. The mother liquorwas then evaporated under reduced pressure to give 4.4 g of3-(N-chloroacetyl-2,6-dimethylphenylamino)-2-butanone O-methyloxime, asan oil. The infrared spectrum of the product showed carbonyl absorptionat 5.95 micron and a strong absorption at 9.6 micron. This product istabulated in Table I as Compound No. 5-B.

Example 6--Preparation ofalpha-(N-chloroacetyl-2,6-dimethylphenylamino)acetaldehyde

A solution of 2 galpha-(N-chloroacetyl-2,6-dimethylphenylamino)acetaldehyde diethylacetal(U.S. Pat. No. 3,966,811) and 0.1 g p-toluenesulfonic acid in 50 mlacetone was heated under reflux for 3 hours. The reaction mixture wasevaporated under reduced pressure, diluted with ethyl ether, washed withwater, washed with sodium bicarbonate solution and evaporated to an oil.Analysis of the oil indicated the presence of about 50% of the startingdiethylacetal.

The oil, 3 g of additional diethylacetal and 0.3 g of additionalp-toluenesulfonic acid in 50 ml acetone were heated under reflux for 10hours. The reaction mixture was worked up as described above to give anoil. The oil was chromatographed through a silica gel column. Thedesired product (2.6 g) was eluted with 10% ethyl ether in hexane. Theinfrared spectrum of the product showed strong carbonyl absorption at5.8 micron and 6.0 micron. The product is tabulated in Table I asCompound No. 8-A.

Example 7--Preparation ofalpha-(N-chloroacetyl-2-methyl-6-ethylphenylamino)acetaldehyde oxime

A solution of 5 g (0.2 mol)alpha-(N-chloroacetyl-2-methyl-6-ethylphenylamino)acetaldehyde, 3.3 g(0.04 mol) hydroxylamine hydrochloride and 3.4 g (0.04 mol) sodiumbicarbonate in 50 ml ethanol was heated at 40° C. for 40 minutes. Thereaction mixture was filtered, evaporated under reduced pressure,diluted with ethyl ether, filtered again and evaporated under reducedpressure to give 5.5 g of a yellow oil which crystallized to a solid onstanding. The crude solid was recrystallized from ethyl ether/hexane togive 3.2 g of the product as a white solid, m.p. 113°-115° C. Theproduct is tabulated in Table I as Compound No. 11.

Example 8--Preparation ofbeta-(N-chloroacetyl-2,6-dimethylphenylamino)propionaldehyde

A solution of 33.9 g (0.28 mol) dimethylaniline, 50 g (0.3 mol)beta-chloropropionaldehyde diethylacetal, 45 g (0.3 mol) sodium iodideand 48.3 g (0.35 mol) potassium bicarbonate in 300 ml ethanol was heatedunder reflux for 7 hours. The reaction mixture was cooled, filtered andevaporated under reduced pressure to give 28.1 g of an amber oil. Theoil was distilled (pot temperature 133°-135° C. at 0.5 mm Hg) to give16.1 g of beta-(2,6-dimethylphenylamino)propionaldehyde diethylacetal.

An 8.6-g (0.076-mol) sample of chloroacetyl chloride was added dropwiseto a solution of 16 g (0.06 mol)beta-2,6-dimethylphenylamino)propionaldehyde diethylacetal and 6 g(0.076 mol) pyridine in 60 ml ethyl acetate. A salt immediatelyprecipitated. The reaction mixture was stirred at about 25° C. for about18 hours. The reaction mixture was filtered and the filtrate wasevaporated under reduced pressure to give an oil. The oil was mixed with100 ml acetone, 25 ml water and about 0.5 g p-toluenesulfonic acid. Theresulting solution was stirred for 2 hours at 25° C., diluted withwater, and extracted with ethyl ether. The ether extracts wereevaporated to give a pale yellow oil. The yellow oil was dissolved indichloromethane, dried over magnesium sulfate, treated with silica,filtered and evaporated to give 12.3 g of an oil which partiallycrystallized to give the product. Infrared analysis showed amidecarbonyl absorption at 6.0 micron and aldehyde carbonyl absorption at5.8 micron. The product is tabulated in Table I as Compound No. 13-A.

Example 9--Preparation ofbeta-(N-chloroacetyl-2,6-dimethylphenylamino)propionaldehydeO-methyloxime

A 2.0-g (0.024-mol) sample of methoxyamine hydrochloride was addedslowly to a slurry of 3.0 g (0.012 mol)beta-(N-chloroacetyl-2,6-dimethylphenylamino)propionaldehyde and 2.0 g(0.02 mol) sodium bicarbonate in 75 ml ethanol. The reaction mixture wasstirred at about 35° C. for 2 hours, filtered and evaporated to give 2.9g of the product as an oil. The product is tabulated in Table I asCompound No. 13-B.

Example 10--Preparation of3-(N-chloroacetyl-2,6-dimethylphenylamino)-butan-2-one O-methyloxime

A solution of 484.8 g (4 mols) 2,6-dimethylaniline and 422.8 g (4.8mols) 3-hydroxy-2-butanone in 1200 ml benzene was heated under refluxfor 21 hours in a reaction vessel equipped with a Dean-Stark trap. Thereaction mixture was then cooled, washed with four 600-ml portions ofwater, slurried with silica gel, filtered and evaporated under reducedpressure to give 722 g of 3-(2,6-dimethylphenylamino)-2-butanone, as anorange oil. The infrared spectrum of the product showed strong carbonylabsorption at 6.3 microns.

A sample of 50.5 g triethylamine was added dropwise to a solution of50.1 g (0.6 mol) methoxyamine hydrochloride in 75 ml dichloromethane at9°-20° C. To the resulting solution was added about one-half of a 95.6-g(0.5-mol) sample of 3-(2,6-dimethylphenylamino)-2-butanone. The reactiontemperature rose from 16° C. to 30° C. The reaction mixture was cooledin an ice bath, and the remaining 3-(2,6-dimethylphenylamino)-2-butanonewas added dropwise. The reaction mixture was then stirred about 18 hoursat about 20° C., washed with 50 ml of water and evaporated under reducedpressure to give 100.3 g of 3-(2,6-dimethylphenylamino)-2-butanoneO-methyloxime, as an oil. The nuclear magnetic resonance spectrum showeda sharp 3-proton singlet (--OCH₃) at 3.9 ppm (relative totetramethylsilane) and a sharp 6-proton singlet (2,6-dimethyl groups) at2.2 ppm.

A sample of 54.2 g (0.048 mol) chloroacetyl chloride and a sample of34.8 g (0.44 mol) pyridine was added over a 25-minute period to asolution of 97.0 g (0.44 mol) 3-(2,6-dimethylphenylamino)-2-butanoneO-methyloxime maintained at 45° C. in 500 ml benzene. The pyridine wasadded slightly faster than the chloroacetyl chloride. The reactiontemperature rose to about 50°-58° C. during the addition. The reactionmixture was then cooled, washed with water, washed with 5% aqueoussodium bicarbonate solution, stirred with silica gel, filtered andevaporated under reduced pressure to give 111.5 g of3-(N-chloroacetyl-2,6-dimethylphenylamino)-2-butanone O-methyloxime, asan oil. The infrared spectrum of the product showed carbonyl absorptionat 5.9 micron and O--CH₃ absorption at 9.5 micron. The product istabulated in Table I as Compound No. 5-B.

Example 11--Preparation of3-(N-chloroacetyl-2,6-dimethylphenylamino)-2-butanone O-methylcarbamyloxime

3-(N-chloroacetyl-2,6-dimethylphenylamino)-2-butanone oxime (2.6 g) wasdissolved in 75 ml methylene chloride and 5 drops of triethylamine wereadded. To this mixture was added 2.6 g methylisocyanate and the solutionwas stirred at room temperature. The solution was refluxed for 5 minutesand solvent was stripped. The oil was crystallized in ethanol-water toyield 3 g tan product. This product is tabulated as Compound No. 17 inTable I.

Example 12--Preparation of3-(N-chloroacetyl-2,6-dimethylphenylamino)-2-butanone-O-phenylcarbamyloxime

Following the procedure of Example 11, 3 g of3-(N-chloroacetyl-2,6-dimethylphenylamino)-2-butanone oxime, 3 gphenylisocyanate and 5 drops triethylamine in 100 ml methylene chloridewere stirred, refluxed and worked up to yield the title product, m.p.115°-117° C. This product is tabulated as Compound No. 18 in Table I.

Example 13--Preparation of3-(N-chloroacetyl-2,6-dimethylphenylamino)-2-butanone O-benzyl oxime

To a solution of 5.4 g of 3-(2,6-dimethylphenylamino)-2-butanoneO-benzyl oxime and 1.6 g pyridine in 100 ml ethyl acetate was addeddropwise over 10 minutes 2.3 g chloroacetyl chloride. The solution wasstirred for an additional 30 minutes at room temperature and poured into1 liter of water. The mixture was extracted with methylene chloride(4×75 ml). The extracts were dried (MgSO₄), purified on silica gel,stripped of solvent to yield 6.3 g light amber oil. The oil wascentrifuged and the 5.7 g of the title product was pipetted from thetube. This product is tabulated as Compound No. 19 in Table I.

Example 14--Preparation of3-(N-chloroacetyl-2,6-dimethylphenylamino)-2-butanone O-allyl oxime

To a solution of 3-(2,6-dimethylphenylamino)-2-butanone O-allyl oxime(4.5 g) in 75 ml ethyl acetate and 1.6 g pyridine was added dropwise 2.3g chloroacetyl chloride. The mixture was stirred for 15 minutes, andpoured into 1 liter of water. The organic phase was collected, dilutedwith 100 ml ether, washed with water, dried (MgSO₄), treated with silicagel and stripped of solvent to yield 4.9 g yellow oil. The oil waschromatographed on silica gel (125 g) with elution by 3:1 CH₂ Cl₂:hexane followed by 5% acetone:CH₂ Cl₂, to yield 2.5 g of the titleproduct. This compound is tabulated as Compound No. 20 in Table I.

Example 15--Preparation of3-(N-chloroacetyl-2,6-dimethylphenylamino)-1-methyoxypropan-2-oneO-methyl oxime

3-(N-chloroacetyl-2,6-dimethylphenylamino)-1-methoxypropan-2-one (3.0 g)was dissolved in 50 ml dry ethanol and methoxyamine hydrochloride (1.25g) and potassium carbonate (2.1 g) were added. The mixture was stirredovernight at room temperature, warmed on a water bath for 10 minutes andpoured into 500 ml water. Extraction with methylene chloride followed bydrying (MgSO₄) and stripping of the solvent yielded 3.0 g of colorlessoil, the title compound. This compound is tabulated as Compound No. 20in Table I.

The compounds tabulated in Table I were prepared by procedures similarto those of Examples 1-15. The structure of each compound tabulated inTable I was confirmed by nuclear magnetic resonance and/or infraredspectroscopy.

UTILITY

The compounds of the present invention are, in general, herbicidal inboth pre- and post-emergent applications. For pre-emergent control ofundesirable vegatation, the herbicidal compounds will be applied inherbicidally effective amounts to the locus or growth medium of thevegetation, e.g., soil infested with seeds and/or seedlings of suchvegetation. Such application will inhibit the growth of or kill theseeds, germinating seeds and seedlings. For post-emergent applications,the herbicidal compounds will be applied directly to the foilage andother plant parts. Generally, the herbicidal compounds of the inventionare effective against weed grasses as well as broad-leaved weeds. Somemay be selective with respect to the type of application and/or type ofweed. The oxime compounds are particularly effective as pre-emergentherbicides against weed grasses.

The oxime compounds, when applied to growing plants above the ground insuch an amount that the compounds will not kill beneficial plants, alsoshow efficient plant growth regulating or retarding effects and may beadvantageously employed, for example, to prevent or retard the growth oflateral buds in plants and to promote the thinning out of superfluousfruits in various fruit trees.

The oxime compounds can be applied in any of a variety of compositions.In general, the compounds can be extended with a carrier material of thekind used and commonly referred to in the art such as inert solids,water and organic liquids.

The compounds will be included in such compositions in sufficient amountso that they can exert an herbicidal or growth-regulating effect.Usually from about 0.5 to 95% by weight of the compounds are included insuch formulations.

Solid compositions can be made with inert powders. The compositions thuscan be homogeneous powders that can be used as such, diluted with inertsolids to form dusts, or suspended in a suitable liquid medium for sprayapplication. The powders usually comprise the active ingredient admixedwith minor amounts of conditioning agent. Natural clays, eitherabsorptive, such as attapulgite, or relatively non-absorptive, such aschina clays, diatomaceous earth, synthetic fine silica, calcium silicateand other inert solid carriers of the kind conventionally employed inpowdered herbicidal compositions can be used. The active ingredientusually makes up from 0.5-90% of these powder compositions. The solidsordinarily should be very finely divided. For conversion of the powdersto dusts, talc, pyrophyllite, and the like, are customarily used.

Liquid compositions including the active compounds described above canbe prepared by admixing the compound with a suitable liquid diluentmedium. Typical of the liquid media commonly employed are methanol,benzene, toluene, and the like. The active ingredient usually makes upfrom about 0.5 to 50% of these liquid compositions. Some of thesecompositions are designated to be used as such, and others to beextended with large quantities of water.

Compositions in the form of wettable powders or liquids can also includeone or more surface-active agents, such as wetting, dispersing oremulsifying agents. The surface-active agents cause the compositions ofwettable powders or liquids to disperse or emulsify easily in water togive aqueous sprays.

The surface-active agents employed can be of the anionic, cationic ornonionic type. They include, for example, sodium long-chaincarboxylates, alkyl aryl sulfonates, sodium lauryl sulfate, polyethyleneoxides, lignin sulfonates and other surface-active agents.

When used as a pre-emergent treatment, it is desirable to include afertilizer, an insecticide, a fungicide or another herbicide.

The amount of oxime compound or composition administered will vary withthe particular plant part or plant growth medium which is to becontacted, the general location of application--i.e., sheltered areassuch as greenhouses, as compared to exposed areas such as fields--aswell as the desired type of control. Generally for both pre- andpost-emergent herbicidal control, the compounds of the invention areapplied at rates of 0.2 to 60 kg/ha, and the preferred rate is in therange 0.5 to 40 kg/ha. For plant growth regulating or retardingactivity, it is essential to apply the oxime compounds at aconcentration not so high as to kill the plants. Therefore, theapplication rates for plant growth regulating or retarding activity willgenerally be lower than the rates used for killing the plants.Generally, such rates vary from 0.1 to 5 kg/ha, and preferably from 0.1to 3 kg/ha.

Herbicidal and plant-growth-regulating tests on representative compoundsof the invention were made using the following methods.

Pre-Emergent Herbicidal Test

An acetone solution of the test compound was prepared by mixing 375 mgof the compound, 118 mg of a non-ionic surfactant and 18 ml of acetone.10 ml of this solution was added to 40 ml of water to give the testsolution.

Seeds of the test vegetation were planted in a pot of soil and the testsolution was sprayed uniformly onto the soil surface at a dose of 27.5micrograms/cm². The pot was watered and placed in a greenhouse. The potwas watered intermittently and observed for seedling emergence, healthof emerging seedlings, etc., for a 3-week period. At the end of thisperiod, the herbicidal effectiveness of the compound was rated based onthe physiological observations. A 0-to-100 scale was used, 0representing no phytotoxicity, 100 representing complete kill. Theresults of these tests appear in Table II.

Post-Emergent Herbicidal Test

The test compound was formulated in the same manner as described abovefor the pre-emergent test. This formulation was uniformly sprayed on 2similar pots of 24-day-old plants (approximately 15 to 25 plants perpot) at a dose of 27.5 microgram/cm². After the plants had dried, theywere placed in a greenhouse and then watered intermittently at theirbases, as needed. The plants were observed periodically for phytotoxiceffects and physiological and morpholigical responses to the treatment.After 3 weeks, the herbicidal effectiveness of the compound was ratedbased on these observations. A 0-to-100 scale was used, 0 representingno phytotoxicity and 100 representing complete kill. The results ofthese tests appear in Table II.

AXILLARY BUD GROWTH INHIBITION OF PINTO BEAN PLANTS

Compound Nos. 1-b and 5-B were tested to determine theirplant-growth-retarding effects on anxillary bud growth of pinto beans.

Idaho pinto bean plants (13-16 days old) having monofoliate leaves fullydeveloped and first trifoliates beginning to unfold were used. Allgrowth 5 mm above the monofoliate leaf node was removed with forceps 1to 4 hours prior to treatment with the test compounds. Four plants wereused for each test compound.

A 625-ppm solution of the test compound in a 2% aqueous acetone solutioncontaining a small amount of a non-ionic surfactant was sprayed onto thepinto bean plants until runoff. After drying, the treated plants weretransferred to a greenhouse maintained at 20°-23° C. and watered atregular intervals. Twelve days after treatment, the bud growth at theaxil of the monofoliate leaf was determined and expressed as percentinhibition of anxillary bud growth as compared to untreated checkplants. The results are reported in Table III.

AXILLARY BUD GROWTH INHIBITION OF TOBACCO

Compound Nos. 1-B and 5-B were tested to determine theirplant-growth-regulating effects on anxillary bud growth of tobacco.

Tobacco plants (9-10 weeks old, Glurk cultivar), with their top 15 cmcut off 24 hours before treatment, were used. Three plants were used foreach test compound.

A 5% solution of the test compound and a small amount of a non-ionicsurfactant were diluted with water to give a 400-ppm test solution. Thetobacco plants were sprayed with the test solution until runoff. Theplants were then incubated in a greenhouse maintained between 20°-23° C.and watered at regular intervals. After 18-28 days, the percent budinhibition was determined by comparing the axillary buds at the topthree nodes of each plant with those of untreated check plants. Theresults are tabulated in Table III.

                                      TABLE I                                     __________________________________________________________________________    Compounds of the formula                                                       ##STR13##                                                                                                           Elemental Analysis                                                            C       H       N(Cl)                  No.                                                                              Ar          Y      R.sup.2                                                                               R.sup.3                                                                         n m.p., °C.                                                                   Calc.                                                                             Found                                                                             Calc.                                                                             Found                                                                             Calc.                                                                             Found              __________________________________________________________________________    1A 2,6-(CH.sub.3).sub.2φ                                                                 O      CH.sub.2 CH.sub.2 CH.sub.2                                                              0 79-82                (12.7)                                                                            (13.5)             1B 2,6-(CH.sub.3).sub.2φ                                                                 NOCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2                                                              0 oil                  (11.5)                                                                            (12.1)             2  2,6-(CH.sub.3).sub.2φ                                                                 NOC.sub.2 H.sub.5                                                                    CH.sub.2 CH.sub.2 CH.sub.2                                                              0 oil  63.1                                                                              62.5                                                                              7.4 7.0 8.7 8.3                3  2,3-(CH.sub.3).sub.2φ                                                                 NOCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2                                                              0 oil  62.1                                                                              61.9                                                                              6.9 7.0 9.1 8.9                4  2,6-(C.sub.2 H.sub.5).sub.2φ                                                          NOCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2                                                              0 oil  64.1                                                                              59.0                                                                              7.5 7.2 8.3 8.0                5A 2,6-(CH.sub.3).sub.2φ                                                                 O      CH.sub.3                                                                             CH.sub.3                                                                         0 78-82                                                                              62.8                                                                              64.2                                                                              6.7 6.9 5.2 5.4                5B 2,6-(CH.sub.3).sub.2φ                                                                 NOCH.sub.3                                                                           CH.sub.3                                                                             CH.sub.3                                                                         0 oil  60.6                                                                              60.4                                                                              7.1 7.0 9.4 8.8                6  2-CH.sub.36-C.sub.2 H.sub.5φ                                                          NOCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2                                                              0 oil  63.2                                                                              67.2                                                                              7.2 7.5 8.7 8.0                7A 2,6-(CH.sub.3).sub.2φ                                                                 O      (CH.sub.2).sub.4                                                                        0 110-112              (11.5)                                                                            (11.0)             7B 2,6-(CH.sub.3).sub.2φ                                                                 NOCH.sub.3                                                                           (CH.sub.2).sub.4                                                                        0 oil  63.2                                                                              60.7                                                                              7.2 7.5 8.7 5.4                8A 2,6-(C.sub.2 H.sub.5).sub.2φ                                                          O      CH.sub.3                                                                             CH.sub.3                                                                         0 oil  65.0                                                                              64.7                                                                              7.5  7.6                                                                              4.7 4.7                8B 2,6-(C.sub.2 H.sub.5).sub.2φ                                                          NOCH.sub.3                                                                           CH.sub.3                                                                             CH.sub.3                                                                         0 oil  62.9                                                                              67.1                                                                              7.7 8.0 8.6 7.9                9A 2,6-(CH.sub.3).sub.2φ                                                                 NOCH.sub.3                                                                           H      H  0 oil                  (14.8)                                                                            (15.6)             9B 2,6-(CH.sub.3).sub.2φ                                                                 O      H      H  0 55-57                                                                              58.1                                                                              59.1                                                                              6.3 6.5 10.4                                                                              10.6               10 2,6-(CH.sub.3).sub.2φ                                                                 NOCH.sub.3                                                                           H      H  0 oil  60.7                                                                              60.6                                                                              7.4 7.4 9.4 8.5                11 2-CH.sub. 3 6-C.sub.2 H.sub.5φ                                                        NOCH.sub.3                                                                           H      H  0 oil  59.5                                                                              59.1                                                                              6.7 6.7 9.9 9.5                12 2-CH.sub. 3 6-C.sub.2 H.sub.5φ                                                        NOH    H      H  0 113-115                                                                            58.1                                                                              59.8                                                                              6.3 6.8 10.4                                                                              10.9               13A                                                                              2,6-(CH.sub.3).sub.2φ                                                                 O      H      H  1 oil  61.5                                                                              59.8                                                                              6.3 6.3 5.5 5.3                13B                                                                              2,6-(CH.sub.3).sub.2φ                                                                 NOCH.sub.3                                                                           H      H  1 oil  59.5                                                                              61.6                                                                              6.7 7.0 9.9 8.6                14 2,6-(CH.sub.3).sub.2φ                                                                 NOCH.sub.3                                                                           H      φ                                                                            0 77-80                                                                              66.2                                                                              67.5                                                                              6.1 6.4 8.1 8.1                15A                                                                              2,6-(CH.sub.3).sub.2φ                                                                 O      H      CH.sub.3                                                                         0   97- 98.5           (14.0)                                                                            (13.4)             15B                                                                              2,6-(CH.sub.3).sub.2φ                                                                 NOCH.sub.3                                                                           H      CH.sub.3                                                                         0 59-61                                                                              59.5                                                                              59.6                                                                              6.7 6.7 9.9 9.8                16A                                                                              2,6-(C.sub.2 H.sub.5).sub.2φ                                                          O      H      CH.sub.3                                                                         0 65-66                (12.6)                                                                            (12.6)             16B                                                                              2,6-(C.sub.2 H.sub.5).sub.2φ                                                          NOCH.sub.3                                                                           H      CH.sub.3                                                                         0 oil                  (11.4)                                                                            (10.9)             17 2,6-(CH.sub.3).sub.2φ                                                                 (1)    CH.sub.3                                                                             CH.sub.3                                                                         0 102-114                                                                            56.6                                                                              57.6                                                                              6.5 6.6 12.4                                                                              12.0               18 2,6-(CH.sub.3).sub.2φ                                                                 (2)    CH.sub.3                                                                             CH.sub.3                                                                         0 115-117                                                                            62.8                                                                              63.3                                                                              6.0 6.4 10.5                                                                              10.5               19 2,6-(CH.sub.3).sub.2φ                                                                 NOCH.sub.2 φ                                                                     CH.sub.3                                                                             CH.sub.3                                                                         0 oil  67.7                                                                              64.2                                                                              6.7 6.6 7.5 7.4                20 2,6-(CH.sub.3).sub.2φ                                                                 (3)    CH.sub.3                                                                             CH.sub.3                                                                         0 oil  63.3                                                                              64.7                                                                              7.1 7.4 8.7 9.3                21 2,6-(CH.sub.3).sub.2φ                                                                 NOCH.sub.3                                                                           H      (4)                                                                              0 oil  57.6                                                                              58.3                                                                              6.7 7.0 9.0 8.5                __________________________________________________________________________     ##STR14##                                                                     ##STR15##                                                                     (3)NOCH.sub.2 CHCH.sub.2                                                      (4)CH.sub. 3 OCH.sub.2?                                                  

                  TABLE II                                                        ______________________________________                                        Herbicidal Effectiveness                                                      % Control - Pre/Post                                                          No.  L       M       P       C     W       O                                  ______________________________________                                        1A*  0/0     0/0     0/0     0/0   0/0     0/0                                1B   68/35   80/25   90/30   100/65                                                                              100/80  80/20                              2    23/--   7/--    17/--   98/-- 100/--  68/--                              3    0/--    0/--    45/--   90/-- 99/--   10/--                              4    20/--   0/--    20/--   75/-- 98/--   47/--                              5A   0/0     0/0     0/0     85/0  100/0   80/0                               5B   82/--   47/--   96/--   98/-- 100/--  92/--                              6    30/--   0/--    7/--    80/-- 99/--   3/--                               7A   0/0     0/0     0/0     0/0   0/0     0/0                                7B   73/--   0/--    0/--    0/--  10/--   3/--                               8A   20/0    20/0    35/0    85/40 85/60   40/25                              8B   10/40   15/20   85/40   72/75 100/80  70/55                              9A*  0/0     0/0     0/0     85/0  100/0   55/0                               9B   100/45  40/25   100/0   97/80 97/80   97/35                              10   25/20   30/25   95/25   97/80 99/80   95/45                              11   40/55   40/30   75/35   99/80 100/85  98/30                              12   35/35   35/40   50/40   98/80 100/80  95/20                              13A  0/0     0/0     0/0     0/0   0/0     0/0                                13B  0/20    0/25    0/0     97/80 97/80   70/25                              14   0/0     0/0     0/0     75/10 90/70   0/25                               15A  50/0    55/0    55/0    100/0 100/0   75/0                               16A  15/0    0/0     0/0     93/20 --/40   80/0                               17   0/0     0/0     0/0     93/30 95/65   0/25                               18   0/0     0/0     0/0     97/40 95/75   35/15                              20   15/0    15/0    45/0    95/40 95/75   93/60                              ______________________________________                                         *33 micrograms/cm.sup.2 dosage.                                               L = Lambsquarter (Chenopodium album)                                          M = Mustard (Brassica arvensis)                                               P = Pigweed (Amaranthus retroflexus)                                          C = Crabgrass (Digitaria sanguinalis)                                         W = Watergrass (Echinochloa crusgalli)                                        O = Wild Oats (Avenua fatua)                                             

                  TABLE III                                                       ______________________________________                                        Bud Inhibition                                                                No.          Pinto Bean                                                                              Tobacco                                                ______________________________________                                        1-B          75%       80%                                                    5-B          58%       90%                                                    ______________________________________                                    

What is claimed is:
 1. A compound having the formula ##STR16## whereinAr is phenyl or phenyl substituted with 1 to 4 of the same or differentsubstituents selected from fluoro, chloro, bromo, iodo, or alkyl of 1 to4 carbon atoms, or substituted with 1 to 2 of the same or differentsubstituents selected from alkoxy of 1 to 4 carbon atoms, nitro orhaloalkyl of 1 to 2 carbon atoms and 1 to 3 of the same or differenthalogens selected from fluoro, chloro, bromo or iodo;R¹ is halomethyl of1 to 3 of the same or different halogens selected from fluoro, chloro,bromo or iodo; R² and R³ are joined together to form a carbocyclic ringof 5 to 6 carbon atoms; R⁴ is hydrogen or alkyl of 1 to 6 carbon atoms;n is 0 or 1; and m is 0 or
 1. 2. A compound according to claim 1 whereinAr is 2,6-dialkylphenyl, R¹ is monohalomethyl, n is 0 and, R⁴ ishydrogen.
 3. The compound of claim 2 wherein R² and R³ together aretrimethylene or tetramethylene.
 4. A compound according to claim 2wherein Ar is 2,6-dimethylphenyl, R¹ is chloromethyl, m=1 and R² and R³together form a trimethylene group.